Substituted sulphonylamino(thio)carbonyl compounds as herbicides

ABSTRACT

The invention relates to novel substituted sulphonylamino(thio)carbonyl compounds of the formula (I)                    
     in which 
     A represents oxygen, sulphur, NH, N-alkyl, N-aryl, —CH═N—, or —N═CH—or —CH═CH—, 
     Q represents oxygen or sulphur, 
     R 1  represents respectively optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl, 
     R 2  represents cyano, nitro, halogen or represents respectively optionally substituted alkyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl, alkylsulphonyl, alkenyl, alkinyl, alkenyloxy or alkinyloxy, and 
     R 3  represents respectively optionally substituted heterocyclyl having 5 ring members of which at least one represents oxygen, sulphur or nitrogen and a further one to three may represent nitrogen, 
     (except for certain individual prior art compounds), furthermore to salts of novel compounds of the formula (I), to various processes and novel intermediates for preparing the novel compounds and to their use as herbicides.

The invention relates to novel substituted sulphonylamino(thio)carbonylcompounds, to a plurality of-processes and novel intermediates for theirpreparation and to their use as herbicides.

It is already known that certain sulphonylaminocarbonyl compounds suchas, for example, the compoundsN-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,2,4-oxadiazole-3-carboxamide(cf EP 569810, Example 204),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-oxazole-2-carboxamide(cf. EP 569810, Example 239),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-methyl-oxazole-2-carboxamide(cf. EP 569810, Example 278),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-ethyl-5-methyl-oxazole-2-carboxamide(cf. EP 569810, Example 329),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-oxazole-4-carboxarnide(cf. EP 569810, Example 366),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-thiazole-2-carboxamide(cf. EP 569810, Example 441),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-4-methylthio-thiazole-2-carboxamide(cf. EP 569810, Example 532),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2,5-dimethyl-thiazole-4-carboxamide(cf. EP 569810, Example 576),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2-chloro-thiazole-5-carboxamide(cf. EP 569810, Example 607),N-(2-chloro-6-methoxy-carbonyl-phenylsulphonyl)-1,3,4-oxadiazole-2-carboxamide (cf. EP 569810, Example 641),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-thiadiazole-2-carboxamide(cf. EP 569810, Example 701),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-chloro-1,3,4-thiadiazole-2-carboxamide(cf. EP 569810, Example 735),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,3,4-thiadiazole-2-carboxamide(cf. EP 569810, Example 757),N-(2-chloro-6-methoxy-carbonyl-phenylsulphonyl)-5-methyl-isoxazole-3-carboxamide(cf. EP 569810, Example 791),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-3-carboxamide(cf. EP '569810, Example 861),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-5-carboxamide(cf. EP 569810, Example 871),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-4-carboxamide(cf. EP 569810, Example 918) andN-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-3,5-dimethyl-isoxazole-4-carboxamide(cf. EP 569810, Example 925) have herbicidal properties (cf. also EP341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266, DE4029753). However, the activity of these compounds is not satisfactoryin every respect.

This invention, accordingly, provides the novel substitutedsulphonylamino(thio)carbonyl compounds of the general formula (I),

in which

A represents oxygen, sulphur, NH, N-alkyl, N-aryl, —CH═N— or —N═CH—, or—CH═CH—,

Q represents oxygen or sulphur,

R¹ represents respectively optionally substituted alkyl, alkenyl,alkinyl. cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl orheterocyclylalkyl,

R² represents cyano, nitro, halogen or represents respectivelyoptionally substituted alkyl, alkoxy, alkoxycarbonyl, alkylthio,alkylsulphinyl, alkyl-sulphonyl, alkenyl, alkinyl, alkenyloxy oralkinyloxy, and

R³ represents respectively optionally substituted heterocyclyl having 5ring members of which at least one represents oxygen, sulphur ornitrogen and a further one to three may represent nitrogen,

and salts of compounds of the formula (I),

except for the prior art compoundsN-(2-chloro-6-methoxycarbonyl-phenyl-sulphonyl)-5-phenyl-1,2,4-oxadiazole-3-carboxamide(cf. EP 569810, Example 204),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-oxazole-2-carboxamide(cf. EP 569810, Example 239),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-methyl-oxazole-2-carboxamide(cf. EP 569810, Example 278),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-ethyl-5-methyl-oxazole-2-carboxamide(cf. EP 569810, Example 329),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-oxazole-4-carboxamide(cf. EP 569810, Example 366),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-thiazole-2-carboxamide(cf. EP 569810, Example 441),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-4-methylthio-thiazole-2-carboxamide(cf. EP 569810, Example 532),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2,5-dimethyl-thiazole-4-carboxamide(cf. EP 569810, Example 576),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2-chloro-thiazole-5-carboxamide(cf. EP 569810, Example 607),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-oxadiazole-2-carboxamide(cf. EP 569810, Example 641),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-thiadiazole-2-carboxamide (cf. EP 569810, Example 701),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-chloro-1,3,4-thiadiazole-2-carboxarnide(cf. EP 569810, Example 735),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,3,4-thiadiazole-2-carboxamide(cf. EP 569810, Example 757),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-3-carboxamide(cf. EP 569810, Example 791),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-3-carboxamide(cf. EP 569810, Example 861),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-5-carboxamide(cf. EP 569810, Example 871),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-4-carboxamide(cf EP 569810, Example 918) andN-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-3,5-dimethyl-isoxazole-4-carboxamide(cf. EP 569810, Example 925) which are excluded by disclaimer.

The novel substituted sulphonylamino(thio)carbonyl compounds of thegeneral formula (I), are obtained when

(a) sulphonamides of the general formula (II)

in which

A, R¹ and R² are each as defined above, are reacted with(thio)carboxylic acid derivatives of the general formula (III)

in which

Q and R³ are each as defined above and

Z represents halogen, alkoxy, aryloxy or arylalkoxy,

if appropriate in the presence of an acid acceptor and if appropriate inthe presence of a diluent,

or when

(b) sulphonyl iso(thio)cyanates of the general formula (IV)

in which

A, Q, R¹ and R² are each as defined above, are reacted with heterocyclesof the general formula (V)

H—R ³  (V)

in which

R³ is as defined above,

if appropriate in the presence of a reaction auxiliary and ifappropriate in the presence of a diluent,

or when

(c) sulphonyl chlorides of the general formula (VI)

in which

A, R¹ and R² are each as defined above, are reacted with heterocycles ofthe general formula (V)

H—R ³  (V)

in which

R³ is as defined above, and metal (thio)cyanates of the general formula(VII)

MQCN  (VII)

in which

Q is as defined above,

if appropriate in the presence of a reaction auxiliary and ifappropriate in the presence of a diluent,

or when

(d) sulphonyl chlorides of the general formula (VI)

in which

A, R¹ and R² are each as defined above,

are reacted with (thio)carboxamides of the general formula (VIII)

in which

Q and R³ are each as defined above,

if appropriate in the presence of an acid acceptor and if appropriate inthe presence of a diluent,

or when

(e) sulphonylamino(thio)carbonyl compounds of the general formula (IX)

in which

A, Q, R¹ and R² are each as defined above and

Z represents halogen, alkoxy, aryloxy or arylalkoxy,

are reacted with heterocycles of the general formula (V)

H—R³  (V)

in which

R³ is as defined above,

if appropriate in the presence of an acid acceptor and if appropriate inthe presence of a diluent,

and the compounds of the formula (I) obtained by processes (a), (b),(c), (d) or (e) are, if desired, converted into salts by customarymethods.

The novel substituted sulphonylamino(thio)carbonyl compounds of thegeneral formula (I) have strong herbicidal activity.

The invention preferably provides compounds of the formula (I) in which

A represents oxygen, sulphur, NH, N-C₁-C₄-alkyl, N-phenyl, —CH═N— or—N═CH— or —CH═CH—,

Q represents oxygen or sulphur,

R¹ represents optionally cyano-, nitro-, halogen- orC₁-C₄-alkoxy-substituted C₁-C₆-alkyl, represents respectively optionallycyano- or halogen-substituted C₂-C₆-alkenyl or C₂-C6-alkinyl, representsrespectively optionally cyano-, halogen- or C₁-C₄-alkyl-substitutedC₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, represents respectivelyoptionally cyano-, nitro-, halogen-, C₁-C₄-alkyl-, C₁-C₄-halogenoalkyl-,C₁-C₄-alkoxy- or C₁-C₄-halogenoalkoxy-substituted phenyl orphenyl-C₁-C₄-alkyl, or represents respectively optionally cyano-,nitro-, halogen-, C₁-C₄-alkyl-, C₁--C₄-halogenoalkyl-, C₁-C₄-alkoxy- orC₁-C₄-halogenoalkoxy-substituted heterocyclyl orheterocyclyl-C₁-C₄-alkyl, where in each case the heterocyclyl group isselected from the group consisting of oxetanyl, thietanyl, furyl,tetrahydrofuryl, thienyl, tetrahydrothienyl, oxazolyl, isoxazolyl,thiazolyl, oxadiazolyl, thiadiazolyl,

R² represents cyano, nitro, halogen, represents respectively optionallycyano-, halogen- or C₁-C₄-alkoxy-substituted C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-alkoxy-carbonyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulphinyl orC₁-C₄-alkylsulphonyl, or represents respectively optionally cyano- orhalogen-substituted C₂-C₄-alkenyl, C₂-C₄-alkinyl, C₂-C₄-alkenyloxy orC₂-C₄-alkinyloxy, and

R³ represents respectively optionally substituted heterocyclyl of theformulae below,

in which

Q¹, Q² and Q³ each represent oxygen or sulphur and

R⁴ represents hydrogen, hydroxyl, amino, cyano, representsC₂-C₁₀-alkylidene-amino, represents optionally fluorine-, chlorine-,bromine-, cyano-, C₁-C₄-alkoxy-, C₁-C₄-alkyl-carbonyl- orC₁-C₄-alkoxy-carbonyl-substituted C₁-C₆-alkyl, represents respectivelyoptionally fluorine-, chlorine- and/or bromine-substituted C₂-C₆-alkenylor C₂-C₆-alkinyl, represents respectively optionally fluorine-,chlorine-, bromine-, cyano-, C₁-C₄-alkoxy- orC₁-C₄-alkoxy-carbonyl-substituted C₁-C₆-alkoxy, C₁-C₆-alkylamino orC₁-C₆-alkyl-carbonyl-amino, represents C₃-C₆-alkenyloxy, representsdi-(C₁--C₄-alkyl)-amino, represents respectively optionally fluorine-,chlorine-, bromine-, cyano- and/or C₁-C₄-alkyl-substitutedC₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-amino orC₃-C₆-cycloalkyl-C₁-C₄-alkyl, or represents respectively optionallyfluorine-, chlorine-, bromine-, cyano-, nitro-, C₁-C₄-alkyl-,trifluoromethyl- and/or C₁-C₄-alkoxy-substituted phenyl or phenyl-C₁-C₄-alkyl,

R⁵ represents hydrogen, hydroxyl, mercapto, amino, cyano, fluorine,chlorine, bromine, iodine, represents optionally fluorine-, chlorine-,bromine-, cyano-, C₁-C₄-alkoxy-, C₁-C₄-alkyl-carbonyl- or C₁-C₄-alkoxy-carbonyl-substituted C₁-C₆-alkyl, represents respectivelyoptionally fluorine-, chlorine- and/or bromine-substituted C₂-C₆-alkenylor C₂-C₆-alkinyl, represents respectively optionally fluorine-,chlorine-, cyano-, C₁-C₄-alkoxy- or C₁-C₄-alkoxy-carbonyl-substitutedC₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-alkylamino orC₁-C₆-alkyl-carbonylamino, represents C₃-C₆-alkenyloxy,C₃-C₆-alkinyloxy, C₃-C₆-alkenylthio, C₃-C₆-alkinylthio,C₃-C₆-alkenylamino or C₃-C₆-alkinylamino, representsdi-(C₁-C₄-alkyl)-amino, represents respectively optionally methyl-and/or ethyl-substituted aziridino, pyrrolidino, piperidino ormorpholino, represents respectively optionally fluorine-, chlorine-,bromine-, cyano- and/or C₁-C₄-alkyl-substituted C₃-C₆-cycloalkyl,C₅-C₆-cycloalkenyl, C₃-C₆-cycloalkyloxy, C₃-C₆-cycloalkylthio,C₃-C₆-cycloalkylamino, C₃-C₆-cycloalkyl-C₁-C₄-alkyl,C₃-C₆-cycloalkyl-C₁-C₄-alkoxy, C₃-C₆-cycloalkyl-C₁-C₄-alkylthio orC₃-C₆-cycloalkyl-C₁-C₄-alkylamino, or represents respectively optionallyfluorine-, chlorine-, bromine-, cyano-, nitro-, C₁-C₄-alkyl-,trifluoromethyl-, C₁-C₄-alkoxy- and/or C₁-C₄-alkoxy-carbonyl-substitutedphenyl, phenyl-C₁-C₄-alkyl, phenoxy, phenyl-C₁-C₄-alkoxy, phenylthio,phenyl-C₁-C₄-alkylthio, phenylamino or phenyl-C₁ -C₄-alkylamino, or

R⁴ and R⁵ together represent optionally branched alkanediyl having 3 toII carbon atoms, furthermore R⁶, R⁷ and R⁸ are identical or differentand each represents hydrogen, cyano, fluorine, chlorine, bromine, orrepresents respectively optionally fluorine-, chlorine-, bromine- or C₁-C₄-alkoxy-substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy,alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkylsulphinyl oralkylsulphonyl having in each case up to 6 carbon atoms or representoptionally cyano-, fluorine-, chlorine-, bromine- orC₁-C₄-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms,

except for the prior art compoundsN-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,2,4-oxadiazole-3-carboxamide(cf. EP 569810, Example 204),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-oxazole-2-carboxamide (cfEP 569810, Example 239),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-methyl-oxazole-2-carboxamide(cf. EP 569810, Example 278),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-ethyl-5-methyl-oxazole-2-carboxamide(cf. EP 569810, Example 329),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-oxazole-4-carboxamide(cf. EP 569810, Example 366),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-thiazole-2-carboxamide(cf. EP 569810, Example 441),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-4-methylthio-thiazole-2-carboxamide(cf. EP 569810, Example 532),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2,5-dimethyl-thiazole-4-carboxamide(cf EP 569810, Example 576),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2-chloro-thiazole-5-carboxamide(cf EP 569810, Example 607),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-oxadiazole-2-carboxamide (cf EP 569810, Example 641),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-thiadiazole-2-carboxamide (cf EP 569810, Example 701),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-chloro-1,3,4-thiadiazole-2-carboxamide(cf. EP 569810, Example 735),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,3,4-thiadiazole-2-carboxamide(cf EP 569810, Example 757),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-3-carboxamide(cf. EP 569810, Example 791),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-3-carboxamide(cf EP 569810, Example 861),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-5-carboxamide(cf. EP 569810,

Example 871),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-4-carboxamide(cf. EP 569810, Example 918) andN-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-3,5-dimethyl-isoxazole-4-carboxamide(cf EP 569810, Example 925) which are excluded by disclaimer.

The invention furthermore preferably provides the sodium, potassium,magnesium, calcium, ammonium, C₁-C₄-alkyl-ammonium,di-(C₁-C₄-alkyl)-ammonium, tri- (C₁-C₄-alkyl)-ammonium,tetra-(C₁-C₄-alkyl)-ammonium, tri-(C₁-C₄-alkyl)-sulphonium, C₅- orC₆-cycloalkyl-ammonium and di-(C₁-C₂-alkyl)-benzyl-ammonium salts ofcompounds of the formula (I) in which A, Q, R¹, R² and R³ are eachpreferably as defined above.

The invention in particular provides compounds of the formula (I), inwhich

A represents sulphur, N-methyl, —CH═N— or —N═CH— or —CH═CH—,

Q represents oxygen or sulphur,

R¹ represents respectively optionally cyano-, fluorine-, chlorine-,methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- ors-butyl, represents respectively optionally cyano-, fluorine- orchlorine-substituted propenyl, butenyl, propinyl or butinyl, representsrespectively optionally cyano-, fluorine-, chlorine-, methyl- orethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl orcyclo-hexylmethyl, represents respectively optionally cyano-, fluorine-,chlorine-, bromine-, methyl-, ethyl-, trifluoromethyl-, methoxy-,ethoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl,phenylmethyl or phenylethyl, or represents respectively optionallycyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, methoxy- orethoxy-substituted heterocyclyl or heterocyclyl-methyl, where in eachcase the heterocyclyl group is selected from the group consisting ofoxetanyl, thietanyl, firyl, tetrahydrofuryl, thienyl, tetrahydrothienyl,

R² represents cyano, fluorine, chlorine, bromine, representsrespectively optionally cyano-, fluorine-, chlorine-, methoxy- orethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl,methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- ori-propoxycarbonyl, methylthio, ethylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl, or representsrespectively optionally cyano-, fluorine- or chlorine-substitutedpropenyl, butenyl, propinyl, butinyl, propenyloxy or propinyloxy, and

R³ represents respectively optionally substituted heterocyclyl of theformulae below,

in which

Q¹, Q² and Q³ each represent oxygen or sulphur and

R⁴ represents hydrogen, hydroxyl, amino, represents respectivelyoptionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substitutedmethyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, representsrespectively optionally fluorine-, chlorine- or bromine-substitutedpropenyl, butenyl, propinyl or butinyl, represents respectivelyoptionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substitutedmethoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino,ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, representspropenyloxy or butenyloxy, represents dimethylamino or diethylamino,represents respectively optionally fluorine-, chlorine-, methyl- and/orethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino,cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl orcyclohexylmethyl, or represents respectively optionally fluorine-,chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted phenylor benzyl,

R⁵ represents hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine,bromine, represents respectively optionally fluorine-, chlorine-,cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl,n-, i-, s- or t-butyl, represents respectively optionally fluorine-,chlorine- or bromine-substituted ethenyl, propenyl, butenyl, propinyl orbutinyl, represents respectively optionally fluorine-, chlorine-,cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy,n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-,i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-,i-, s- or t-butylamino, represents propenyloxy, butenyloxy, propinyloxy,butinyloxy, propenylthio, propadienylthio butenylthio, propinylthio,butinylthio, propenylamino, butenylamino, propinylamino or butinylamino,represents dimethylamino, diethylamino or dipropylamino, representsrespectively optionally fluorine-, chlorine-, methyl- and/orethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy,cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio,cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino,cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl,cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy,cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy,cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio,cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino,cyclopentylmethylamino or cyclohexylmethylamino, or representsrespectively optionally fluorine-, chlorine-, methyl-, trifluoromethyl-,methoxy- and/or methoxycarbonyl-substituted phenyl, benzyl, phenoxy,benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or

R⁴ and R⁵ together represent optionally branched alkanediyl having 3 to11 carbon atoms, furthermore

R⁶, R⁷ and R⁸ are identical or different and each represents hydrogen,cyano, fluorine, chlorine, bromine, or represents respectivelyoptionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, propenyl, butenyl,propinyl, butinyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- ort-butoxy, propenyloxy, butenyloxy, propinyloxy, butinyloxy, methylthio,ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio,butenylthio, propinylthio, butinylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl or ethylsulphonyl, or represents cyclopropyl,

except for the prior art compoundsN-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,2,4-oxadiazole-3-carboxamide (cf. EP 569810, Example 204),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-oxazole-2-carboxamide(cf. EP 569810, Example 239),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-methyl-oxazole-2-carboxamide(cf. EP 569810, Example 278),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-4-ethyl-5-methyl-oxazole-2-carboxamide(cf. EP 569810, Example 329),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-oxazole-4-carboxamide(cf. EP 569810, Example 366),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-ethyl-thiazole-2-carboxamide(cf. EP 569810, Example 441),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-4-methylthio-thiazole-2-carboxamide(cf. EP 569810, Example 532),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2,5-dimethyl-thiazole-4-carboxamide(cf. EP 569810, Example 576),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-2-chloro-thiazole-5-carboxamide(cf. EP 569810, Example 607),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-oxadiazole-2-carboxamide (cf. EP 569810, Example 641),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-1,3,4-thiadiazole-2-carboxamide(cf. EP 569810, Example 701),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-chloro-1,3,4-thiadiazole-2-carboxamide(cf. EP 569810, Example 735),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-phenyl-1,3,4-thiadiazole-2-carboxamide(cf. EP 569810, Example 757),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-3-carboxamide(cf. EP 569810, Example 791),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-3-carboxamide(cf. EP 569810, Example 861),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-isoxazole-5-carboxamide(cf. EP 569810, Example 871),N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-4-carboxamide(cf EP 569810, Example 918) andN-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-3,5-dimethyl-isoxazole-4-carboxamide(cf. EP 569810, Example 925) which are excluded by disclaimer.

A very particularly preferred group of compounds according to theinvention are the compounds of the formula (I) in which

A represents sulphur or —CH═CH—,

Q represents oxygen or sulphur,

R¹ represents methyl, ethyl, n- or i-propyl, 2-cyano-ethyl,2-fluoro-ethyl, 2,2-difluoro-ethyl, 2,2,2-trifluoro-ethyl,2-chloro-ethyl, 2,2-dichloro-ethyl, 2,2,2-trichloro-ethyl,2-methoxy-ethyl, 2-ethoxy-ethyl or oxetanyl,

R² represents fluorine, chlorine, bromine, methyl, ethyl, n- ori-propyl, n-, i- or s- butyl, trifluoromethyl, methoxy, ethoxy, n- ori-propoxy, difluoromethoxy, trifluoromethoxy or trifluoroethoxy, and

R³ represents optionally substituted triazolinyl of the formula below

in which

Q¹ represents oxygen or sulphur and

R⁴ represents respectively optionally fluorine-, chlorine-, methoxy- orethoxy-substituted methyl, ethyl, n- or i-propyl, representsrespectively optionally fluorine- or chlorine-substituted propenyl orpropinyl, represents methoxy, ethoxy, n- or i-propoxy, methylamino,ethylamino, n- or i-propylamino, represents propenyloxy, representsdimethylamino or represents cyclopropyl,

R⁵ represents chlorine or bromine, represents respectively optionallyfluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectivelyoptionally fluorine-, chlorine- or bromine-substituted ethenyl,propenyl, butenyl, propinyl or butinyl, represents respectivelyoptionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substitutedmethoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio,ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino,ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, representspropenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio,propadienylthio, butenylthio, propinylthio, butinylthio, propenylamino,butenylamino, propinylamino or butinylamino, represents dimethylamino,diethylamino or dipropylamino, represents respectively optionallyfluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl,cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy,cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio,cyclopropylarnino, cyclobutylamino, cyclopentylamino, cyclohexylamino,cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl,cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy,cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio,cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio,cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino orcyclohexylmethylamino, or represents respectively optionally fluorine-,chlorine-, methyl-, trifluoromethyl-, methoxy- and/ormethoxycarbonyl-substituted phenyl, benzyl, phenoxy, benzyloxy,phenylthio, benzylthio, phenylamino or benzylamino, or

R⁴ and R⁵ together represent optionally branched alkanediyl having 3 to11 carbon atoms.

The radical definitions listed above, whether general or listed inranges of preference, apply both to the end products of the formula (I)and, correspondingly, to the starting materials and/or intermediatesrequired in each case for the preparation. These radical definitions canbe combined as desired with one another, thus including combinationsbetween the preferred ranges indicated.

Using, for example, 2-fluoro-6-methoxycarbonyl-benzenesulphonamide and5-ethoxy4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazole-3-thioneas starting materials, the course of the reaction in the process (a)according to the invention can be illustrated by the following equation:

Using, for example, 4-chloro-2-ethoxycarbonyl-3-thienylsulphonylisothiocyanate and 5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-oneas starting materials, the course of the reaction in the process (b)according to the invention can be illustrated by the following equation:

Using, for example, 2-methoxycarbonyl-6-methyl-benzenesulphonylchloride, 5-ethylthio-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one andpotassium cyanate as starting materials, the course of the reaction inthe process (c) according to the invention can be illustrated by thefollowing equation:

Using, for example, 2-ethoxycarbonyl-6-trifluoromethyl-benzenesulphonylchloride and 5-methyl-1,2,4-oxadiazole-3-carboxamide as startingmaterials, the course of the reaction in the process (d) according tothe invention can be illustrated by the following equation:

Using, for example,N-(2-chloro-6-methoxycarbonyl-phenylsulphonyl)-O-methyl-urethane and4-methyl-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one as startingmaterials, the course of the reaction in the process (e) according tothe invention can be illustrated by the following equation:

A general definition of the sulphonamides to be used as startingmaterials in the process (a) according to the invention for preparingthe compounds of the formula (1) is given by the formula (II). In theformula (II), A, R¹ and R² each preferably or in particular have thatmeaning which has already been indicated above in connection with thedescription of the compounds of the formula (1) according to theinvention as being preferable or, respectively, particularly preferablefor A, R¹ and R².

The starting materials of the formula (II) are known and/or can beprepared by processes known per se (cf. U.S. Pat. Nos. 4,546,179,5,084,086, 5,157,119, WO 8909214, WO 9115478).

The sulphonamides of the general formula (IIa)

in which

R¹ and R² are each as defined above have not yet been disclosed in theliterature and, as novel compounds, form part of the subject-matter ofthe present application.

The novels sulphonamides of the formula (IIa) are obtained whensulphonyl chlorides of the formula (VIa)

in which

R¹ and R² are each as defined above,

are reacted with ammonia, if appropriate in the presence of a diluentsuch as, for example, water, at temperatures between 0° C. and 50° C.(cf. the Preparation Examples).

The sulphonyl chlorides of the formula (VIa) have not yet been disclosedin the literature; as novel compounds, they also form part of thesubject-matter of the present application.

The novel sulphonyl chlorides of the formula (VIa) are obtained whencorresponding amino compounds of the general formula (X)

in which

R¹ and R² are each as defined above,

are reacted with an alkali metal nitrite such as, for example, sodiumnitrite, in the presence of hydrochloric acid at temperatures between−10° C. and +10° C. and the resulting diazonium salt solution is reactedwith sulphur dioxide in the presence of a diluent such as, for example,dichloromethane, 1,2-dichloro-ethane or acetic acid, and in the presenceof a catalyst such as, for example, copper(I) chloride and/or copper(II)chloride, at temperatures between −10° C. and +50° C. (cf. thePreparation Examples).

The amino compounds of the formula (X) required as intermediates areknown and/or can be prepared by processes known per se (cf. DE 3018134,DE 3804794, EP 298542, Preparation Examples).

A general definition of the (thio)carboxylic acid derivativesfurthermore to be used as, starting materials in the process (a)according to the invention for preparing the compounds of the formula(I) is given by the formula (III). In the formula (III), Q and R³ eachpreferably or in particular have that meaning which has already beenindicated above in connection with the description of the compounds ofthe formula. (I) according to the invention as being preferred or,respectively, particularly preferred for Q and R³; Z preferablyrepresents fluorine, chlorine, bromine, C₁-C₄-alkoxy, phenoxy orbenzyloxy, in particular chlorine, methoxy, ethoxy or phenoxy.

The starting materials of the formula (III) are known and/or can beprepared by processes known per se (cf. EP 459244, EP 341489, EP 422469,EP 425948, EP 431291, EP 507171, EP 534266).

A general definition of the sulphonyl iso(thio)cyanates to be used asstarting materials in the process (b) according to the invention forpreparing the compounds of the formula (I) is given by the formula (IV).In the formula (IV), A, Q, R¹ and R² each preferably or in particularhave that meaning which has already been indicated above in connectionwith the description of the compounds of the formula (I) according tothe invention as being preferred or, respectively, particularlypreferred for A, Q, R¹ and R².

The starting materials of the formula (IV) are known and/or can beprepared by processes known per se (cf. EP 46626, U.S. Pat. No.4,701,535, Preparation Examples).

A general definition of the heterocycles to be used as startingmaterials in the process (b), (c) and (e) according to the invention forpreparing the compounds of the formula (I) is given by the formula (V).In the formula (V), R³ preferably or in particular has that meaningwhich has already been indicated above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred or, respectively, particularly preferredfor R³.

The starting materials of the formula (V) are known and/or can beprepared by known processes (cf. EP 341489, EP 422469, EP 425948, EP431291, EP 507171, EP 534266).

A general definition of the sulphonyl chlorides to be used as startingmaterials in the processes (c) and (d) according to the invention forpreparing the compounds of the formula (1) is given by the formula (VI).In the formula (VI), A, R¹ and R² each preferably or in particular havethat meaning which has already been indicated above in connection withthe description of the compounds of the formula (I) according to theinvention as being preferred or, respectively, particularly preferredfor A, R¹ and R².

The starting materials of the formula (VI) are known and/or can beprepared by processes known per se (cf. U.S. Pat. Nos. 4,546,179,5,084,086, 5,157,119, WO 8909214, WO 9115478, WO 9213845, PreparationExamples). However, as already mentioned, the compounds of the formula(VI) where A=S, i.e. the compounds of the sub-group of the formula(VIa), are novel.

A general definition of the (thio)carboxarnides to be used as startingmaterials in the process (d) according to the invention for preparingthe compounds of the formula (I) is given by the formula (VIII). In theformula (VIII), Q and R³ each preferably or in particular have thatmeaning which has already been indicated above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred or, respectively, particularly preferredfor Q and R³.

The starting materials of the formula (VIII) are known and/or can beprepared by processes known per se (cf. EP 459244).

A general definition of the sulphonylamino(thio)carbonyl compounds to beused as starting materials in the process (e) according to the inventionfor preparing the compounds of the formula (I) is given by the formula(IX). In the formula (IX), A, Q., R¹ and R² each preferably or inparticular have that meaning which has already been indicated above inconnection with the description of the compounds of the formula (I)according to the invention as being preferred or, respectively,particularly preferred for A, Q, R¹ and R²; Z preferably representsfluorine, chlorine, bromine., C₁-C₄-alkoxy, phenoxy or benzyloxy, inparticular represents chlorine, methoxy, ethoxy or phenoxy.

The starting materials of the formula (IX) are known and/or can beprepared by methods known per se.

The processes (a), (b), (c), (d) and (e) according to the invention forthe preparation of the novel compounds of the formula (I) are preferablycarried out using diluents. Suitable diluents in this context arevirtually all inert organic solvents. These include, preferably,aliphatic and aromatic, optionally halogenated hydrocarbons such aspentane, hexane, heptane, cyclohexane, petroleum ether, benzine,ligroin, benzene. toluene, xylene, methylene chloride, ethylenechloride, chloroform, tetrachloromethane, chlorobenzene ando-dichlorobenzene; ethers such as diethyl ether and dibutyl ether,glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran anddioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropylketone and methyl isobutyl ketone; esters such as methyl acetate andethyl acetate; nitrites, for example acetonitrile and propionitrile;amides, for example dimethylformamide, dimethylacetamide andN-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylenesulphone and hexamethylphosphorictriamide.

Suitable reaction auxiliaries and/or acid acceptors for the processes(a), (b), (c), (d) and (e) according to the invention are allacid-binding agents which are conventionally used for such reactions.Preference is given to alkali metal hydroxides, such as, for example,sodium hydroxide and potassium hydroxide, alkaline earth metalhydroxides such as, for example, calcium hydroxide, alkali metalcarbonates and alkoxides, such as sodium carbonate and potassiumcarbonate, sodium tert-butoxide and potassium tert-butoxide, and alsobasic nitrogen compounds, such as trimethylamine, triethylamine,tripropylamine, tributylamine, dilsobutylamine, dicyclohexylamine,ethyldiisopropylamine, ethyldicyclohexylamine, N,N-dimethylbenzylamine,N,N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-,2,4-dimethyl-, 2,6dimethyl-, 2-ethyl-, 4-ethyl- and5-ethyl-2-methyl-pyridine, 1,5-diaza-bicyclo[4,3,0]-non-5-ene (DBN),1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU) and1,4-diazabicyclo-[2,2,2]-octane(DABCO).

The reaction temperatures in the processes (a), (b), (c), (d) and (e)according to the invention can be varied within a relatively wide range.The processes are in general carried out at temperatures of between −20°C. and +150° C., preferably at temperatures between 0° C. and +100° C.

The processes (a), (b), (c), (d) and (e) according to the invention aregenerally carried out under atmospheric pressure. However, it is alsopossible to operate under elevated or reduced pressure.

For carrying out processes (a), (b), (c), (d) and (e) according to theinvention, the starting materials required in each case are in generalemployed in approximately equimolar quantities. However, it is alsopossible to use one of the components employed in each case in arelatively large excess. The reactions are in general carried out in asuitable diluent in the presence of an acid acceptor, and the reactionmixture is stirred for a number of hours at the particular temperaturerequired. Work-up in the case of the processes (a), (b), (c), (d) and(e) according to the invention is in each case carried out by customarymethods (cf. the Preparation Examples).

Salts can be prepared, if desired, from the compounds of the generalformula (I) according to the invention. Such salts are obtained in asimple manner by customary methods of forming salts, for example bydissolving or dispersing a compound of the formula (I) in an appropriatesolvent, for example methylene chloride, acetone, tert-butyl methylether or toluene, and adding an appropriate base. The salts can then—ifdesired after prolonged stirring—be isolated by concentration orfiltration with suction.

The active compounds according to the invention can be used asdefoliants, desiccants, haulm killers and, especially, as weed-killers.By weeds, in the broadest sense, are to be understood all plants whichgrow in locations where they are not wanted. Whether the substancesaccording to the invention act as total or selective herbicides dependsessentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledonousweeds of the genera:

Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga,Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium,Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus,Sonchus, Solanum, Rorippa, Rotala, Lindemia, Lamium, Veronica, Abutilon,Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium,Ranunculus and Taraxacum.

Dicotyledonous cultures of the genera:

Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum,Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca,Cucumis and Cucurbita.

Monocotyledonous weeds of the genera:

Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca,Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum,Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis,Alopecurus and Apera.

Monocotyledonous cultures of the genera:

Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum,Saccharun, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal control of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for controlling weeds inperennial crops, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hop fields, inlawns, turf and pasture-land, and for the selective control of weeds inannual crops.

The compounds of the formula (I) according to the invention areparticularly suitable for the selective control of monocotyledonous anddicotyledonous weeds in monocotyledenous and dicotyledenous crops, bothpre-emergence and post-emergence.

To some extent, the compounds of the formula (I) also have fungicidalactivity, for example against Pyriculariaoryzae on rice.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspo-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants and/or foam formers.

If the extender used is water, it is also possible to use for exampleorganic solvents as auxiliary solvents. Suitable liquid solventsessentially include: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol and their ethers and esters, ketones, such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, and water.

Suitable solid carriers are: for example ammonium salts and groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as finely divided silica, alumina and silicates, suitablesolid carriers for granules are: for example crushed and fractionatednatural rocks such as calcite, marble, pumice, sepiolite and dolomite,and synthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, maize cobs and tobaccostalks; suitable emulsifiers and/or foam-formers are: for examplenonionic and anionic emulsifiers, such as polyoxyethylene fatty acidesters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonatesand protein hydrolysates; suitable dispersants are: for examplelignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, and naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyes, such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

For controlling weeds, the active compounds according to the invention,as such or in the form of their formulations, can also be used asmixtures with known herbicides, finished formulations or tank mixesbeing possible.

Possible components for the mixtures are known herbicides, for exampleanilides, such as diflufenican and propanil; arylcarboxylic acids, suchas dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids,such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr;aryloxy-phenoxy-alkanoicesters, such as, for example, diclofop-methyl,fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl andquizalofop-ethyl; azinones, such as, for example, chloridazon andnorflurazon; carbamates, such as, for example, chlorpropham,desmedipham, phenmedipham and propham; chloroacetanilides, such as, forexample, alachlor, acetochlor, butachlor, metazachlor, metolachlor,pretilachlor and propachlor; dinitroanilines, such as, for example,oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as, forexample, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen,lactofen and oxyfluorfen; ureas, such as, for example, chlorotoluron,diuron, fluometuron, isoproturon, linuron and methabenzthiazuron;hydroxylamines, such as, for example, alloxydim, clethodim, cycloxydim,sethoxydim and tralkoxydim; imidazolinones, such as, for example,imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, such as,for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides, suchas, for example, mefenacet; sulphonylureas, such as arnidosulfuron,bensulfiron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuiron,metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl,thifensulfiron-methyl, triasulfuron and tribenuron-methyl;thiocarbamates, such as, for example, butylate, cycloate, diallate,EPTC, esprocarb, molinate, prosulphocarb, thiobencarb and triallate;triazines, such as atrazine, cyanazine, simazine, simetryne, terbutryneand terbutylazine; triazinones, such as hexazinone, metamitron andmetribuzin; and others, such as, for example, aminotriazole,benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat,dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate,isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

Mixtures with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants. They can also be incorporatedinto the soil before sowing.

The amount of active compound used can vary within a wide range. Itdepends essentially on the nature of the desired effect. In general, theamounts used are between 1 g and 10 kg of active compound per hectare ofsoil surface, preferably between 5 g and 5 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES Example 1

(Process (a))

7.5 g (32 mmol) of 4-methyl-2-methoxycarbonyl-thiophene-3-sulphonamideand 4.9 g (32 mmol) of 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) areadded successively to a solution of 7.9 g (30 mmol) of5-ethoxy-4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazol-3-onein 150 ml of acetonitrile. The reaction mixture is stirred at roomtemperature (about 20° C.) for about 15 hours and subsequentlyconcentrated using water pump vacuum. The residue is then taken up inmethylene chloride and washed with 1hydrochloric acid and then withwater. The organic phase is dried over magnesium sulphate and filtered.The filtrate is concentrated using water pump vacuum and the residue isrecrystallized from isopropanol.

9.2 g (76% of theory) of5-ethoxy-4-methyl-2-(4-methyl-2-methoxycarbonyl-thien-3-yl-sulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-oneof melting point 169° C. are obtained.

Example 2

(Process (b))

2.1 g (8 mmol) of 2-ethoxycarbonyl-4-methyl-thien-3-yl-sulphonylisocyanate are added to a solution of 1.35 g (8 mmol) of4-methyl-5-propargylthio-2,4-dihydro-3H-1,2,4-triazol-3-one in 50 ml ofacetonitrile. The mixture is then heated under reflux for 8 hours andsubsequently concentrated using water pump vacuum, the residue isstirred with diethyl ether and the crystalline product is isolated byfiltration with suction.

1.4 g (40% of theory) of4-methyl-5-propargylthio-2-(2-ethoxycarbonyl-4-methyl-thien-3-yl-sulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-oneof melting point 1 75° C. are obtained.

Example 3

(Process (c))

A solution of 3.8 g (20 mmol) of4-ethoxy-5-ethylthio-2,4-dihydro-3H-1,2,4-triazol-3-one in 50 ml ofacetonitrile is admixed with 6.0 g (24 mmol) of2-methyl-6-methoxy-carbonyl-benzenesulphonyl chloride, 2.6 g (40 mmol)of sodium cyanate and 1.2 g (15 mmol) of pyridine, and the reactionmixture is stirred at room temperature (about 20° C.) for 3 days. Themixture is then diluted with approximately identical volumina ofmethylene chloride and water to about three times its volume and thenmade weakly acidic (pH 3) using IN hydrochloric acid. The organic phaseis separated off, dried over sodium sulphate and filtered. The filtrateis concentrated and the residue is recrystallized from isopropanol.

5.0 g (56% of theory) of4-ethoxy-5-ethylthio-2-(2-methyl-6-methoxy-carbonyl-phenylsulphonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-oneof melting point 135° C. are obtained.

Example 4

(Process (d))

At 20° C. to a maximum of 35° C., 2.0 g (36 mmol) of potassium hydroxidepowder are added to a solution of 1.52 g (12.0 mmol) of5-methyl-1,2,4-oxadiazole-3-carboxamide in 150 ml of dioxane. After 30minutes, about 50 ml of dioxane are distilled off at 30° C. to 35° C.using water pump vacuum. The mixture is subsequently admixed a little ata time with 3.6 g (12.6 mmol) of 4-methyl-2-i-propoxycarbonyl.thiophene-3-sulphonyl chloride and the reaction mixture is stirred atroom temperature (about 20° C.) for about 12 hours. The mixture issubsequently concentrated using water pump vacuum and the residue istaken up in water and acidified using 2N hydrochloric acid. The mixtureis then extracted twice using 100 ml of methylene chloride each time.The combined organic solutions are washed with water, dried overmagnesium sulphate and filtered. The filtrate is concentrated usingwater pump vacuum and the residue is recrystallized from ethanol.

2.3 g (52% of theory) ofN-(4-methyl-2-i-propoxycarbonyl-thien-3-yl-sulphonyl)-5-methyl-1,2,4-oxadiazole-3-carboxamideof melting point 142° C. are obtained.

Similar to Examples 1 to 4, and according to the general description ofthe preparation processes according to the invention, it is alsopossible to prepare for example the compounds of the formula (I) listedin Table 1 below.

TABLE 1 Examples of compounds of the formula (I) Ex. Melting No. A Q R¹R² R³ point (° C.) 5 S O CH₃ CH₃

178 6 S O CH₃ CH₃

192 7 CH═CH O C₂H₅ CH₃

154 8 CH═CH O C₃H₇-i CH₃

124 9 CH═CH O CH₃ CH₃

115 10 CH═CH O C₂H₅ CH₃

85 11 CH═CH O C₃H₇-n CH₃

59 12 CH═CH O C₃H₇-i CH₃

(amorphous) 13 S O CH₃ CH₃

157 14 S O CH₃ CH₃

158 15 CH═CH O C₂H₅ CH₃

168 16 CH═CH O C₃H₇-i CH₃

144 17 CH═CH O C₃H₇-i CH₃

122 18 CH═CH O C₃H₇-i CH₃

167 19 CH═CH O C₃H₇-i CH₃

114 20 CH═CH O C₃H₇-n CH₃

142 21 CH═CH O C₃H₇-n CH₃

106 22 CH═CH O C₃H₇-n CH₃

105 23 CH═CH O C₃H₇-n CH₃

112 24 CH═CH O C₃H₇-n CH₃

115 25 CH═CH O C₃H₇-n CH₃

77 26 CH═CH O C₃H₇-i CH₃

131 27 S O CH₃ CH₃

158 28 S O CH₃ CH₃

175 29 S O CH₃ CH₃

151 30 S O CH₃ CH₃

155 31 S O CH₃ CH₃

184 32 S O CH₃ CH₃

151 33 S O CH₃ CH₃

191 34 S O CH₃ CH₃

142 35 S O CH₃ CH₃

122 36 S O CH₃ CH₃

121 37 S O CH₃ CH₃

187 38 S O CH₃ CH₃

163 39 S O CH₃ CH₃

124 40 S O CH₃ CH₃

162 41 S O CH₃ CH₃

144 42 CH═CH O C₃H₇-i CH₃

125 43 CH═CH O C₃H₇-i CH₃

120 44 CH═CH O C₃H₇-i CH₃

121 45 CH═CH O C₃H₇-n CH₃

118 46 CH═CH O C₃H₇-i CH₃

130 47 CH═CH O C₃H₇-n CH₃

107 48 CH═CH O C₃H₇-n CH₃

87 49 CH═CH O CH₂CF₃ CH₃

113 50 CH═CH O C₃H₇-n CH₃

122 51 S O CH₃ CH₃

137 52 S O CH₃ CH₃

185 53 S O CH₃ CH₃

184 54 S O C₂H₅ CH₃

161 55 S O C₂H₅ CH₃

131 56 S O C₂H₅ CH₃

158 57 S O C₂H₅ CH₃

178 58 S O C₂H₅ CH₃

133 59 S O C₂H₅ CH₃

131 60 S O C₂H₅ CH₃

159 61 S O C₂H₅ CH₃

132 62 S O C₂H₅ CH₃

150 63 S O C₂H₅ CH₃

142 64 S O C₂H₅ CH₃

108 65 S O C₂H₅ CH₃

123 66 S O C₂H₅ CH₃

135 67 S O C₂H₅ CH₃

77 68 S O C₂H₅ CH₃

130 69 S O C₂H₅ CH₃

141 70 S O C₂H₅ CH₃

141 71 CH═CH O C₃H₇-i CF₃

73 72 S O C₂H₅ CH₃

139 73 CH═CH O CH₃ OCF₃

181 74 CH═CH O CH₃ OCF₃

107 75 S O C₃H₇-n CH₃

114 76 S O C₃H₇-i CH₃

152 77 S O C₃H₇-i CH₃

146 78 S O C₃H₇-i CH₃

164 79 S O C₃H₇-n CH₃

167 80 S O C₃H₇-n CH₃

113 81 S O C₃H₇-i CH₃

131 82 S O C₃H₇-i CH₃

173 83 S O C₃H₇-i CH₃

87 84 S O C₃H₇-i CH₃

125 85 S O C₃H₇-i CH₃

127 86 S O C₃H₇-i CH₃

126 87 S O C₃H₇-i CH₃

136 88 S O C₂H₅ CH₃

106 89 S O C₃H₇-n CH₃

117 90 S O C₃H₇-n CH₃

90 91 S O C₃H₇-n CH₃

134 92 S O C₃H₇-n CH₃

141 93 S O C₃H₇-n CH₃

142 94 S O C₃H₇-n CH₃

90 95 S O C₃H₇-n CH₃

119 96 S O C₃H₇-i CH₃

159 97 S O C₃H₇-i CH₃

130 98 S O C₃H₇-i CH₃

145 99 S O C₃H₇-n CH₃

109 100 S O C₃H₇-n CH₃

95 101 S O C₃H₇-n CH₃

84 102 S O C₃H₇-n CH₃

89 103 S O C₃H₇-n CH₃

135 104 S O C₂H₅ CH₃

155 105 S O C₂H₅ CH₃

116 106 S O C₂H₅ CH₃

136 107 S O C₃H₇-i CH₃

135 108 S O C₃H₇-i CH₃

98 109 S O C₃H₇-i CH₃

120 110 S O C₃H₇-i CH₃

140 111 S O C₃H₇i CH₃

137 112 S O C₃H₇-i CH₃

145 113 S O C₃H₇-i CH₃

124 114 S O C₃H₇-n CH₃

108 115 S O C₃H₇-n CH₃

138 116 S O C₃H₇-n CH₃

93 117 S O C₃H₇-n CH₃

130 118 S O C₃H₇-n CH₃

128 119 S O CH₃ CH₃

248 120 CH═CH O CH₃ Cl

78 121 CH═CH O CH₃ CH₃

120 122 CH═CH O CH₃ Cl

68 123 CH═CH O CH₃ CH₃

54 124 CH═CH O CH₃ Cl

147 125 CH═CH O CH₃ CH₃

118 126 CH═CH O CH₃ Cl

63 127 CH═CH O CH₃ Cl

167 128 CH═CH O C₂H₅ Cl

128 129 CH═CH O CH₃ Cl

95 130 CH═CH O CH₃ Cl

153 131 CH═CH O C₂H₅ Cl

145 132 CH═CH O C₃H₇-n Cl

98 133 CH═CH O C₃H₇-n Cl

89 134 CH═CH O C₃H₇-n Cl

110 135 CH═CH O CH₃ OCH₃

175 136 CH═CH O CH₃ OCH₃

190 137 CH═CH O C₃H₇-i Cl

89 138 CH═CH O

CH₃

146 139 CH═CH O

CH₃

158 140 CH═CH O CH₃ CH₃

150 141 CH═CH O CH₃ CH₃

142 142 CH═CH O CH₃ CH₃

145 143 CH═CH O CH₃ CH₃

148 144 CH═CH O CH₃ CH₃

155 145 CH═CH O CH₃ CH₃

185 146 CH═CH O CH₃ CH₃

163 147 CH═CH O CH₃ CH₃

122 148 CH═CH O CH₃ CH₃

137 149 CH═CH O CH₃ CH₃

156 150 CH═CH O CH₃ CH₃

122 151 CH═CH O CH₃ CH₃

166 152 CH═CH O CH₃ CH₃

125 153 CH═CH O CH₃ CH₃

137 154 CH═CH O CH₃ CH₃

179 155 CH═CH O CH₃ CH₃

153 156 CH═CH O CH₃ CH₃

172 157 CH═CH O CH₃ CH₃

124 158 CH═CH O CH₃ CH₃

157 159 CH═CH O CH₃ CH₃

156 160 CH═CH O CH₃ CH₃

138 161 CH═CH O CH₃ CH₃

137 162 CH═CH O CH₃ CH₃

160 163 CH═CH O CH₃ CH₃

139 164 CH═CH O CH₃ CH₃

174 165 CH═CH O CH₃ CH₃

119 166 CH═CH O CH₃ CH₃

158 167 CH═CH O CH₃ CH₃

148 168 CH═CH O CH₃ CH₃

128 169 CH═CH O CH₃ CH₃

145 170 CH═CH O CH₃ CH₃

161 171 CH═CH O CH₃ CH₃

129 172 CH═CH O CH₃ CH₃

136 173 CH═CH O CH₃ CH₃

155 174 CH═CH O CH₃ CH₃

129 175 CH═CH O CH₃ CH₃

150 176 CH═CH O CH₃ CH₃

148 177 CH═CH O CH₃ CH₃

149 178 CH═CH O CH₃ CH₃

99 179 CH═CH O CH₃ CH₃

115 180 CH═CH O CH₃ CH₃

114 181 CH═CH O CH₃ CH₃

125 182 CH═CH O CH₃ CH₃

124 183 CH═CH O CH₃ CH₃

105 184 CH═CH O CH₃ CH₃

131 185 CH═CH O CH₃ CH₃

149 186 S O C₃H₇-n CH₃

187 CH═CH O CH₃ NO₂

180

The compound listed as Example 119 in Table 1 can be prepared forexample as follows:

(Salt formation)

A mixture of 2.0 g (5 mmol) of5-ethoxy-4-methyl-2-(4-methyl-2-methoxy-carbonyl-thien-3-yl-sulfonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-oneand 75 ml of acetonitrile is admixed with 0.17 g (5.5 mmol) of sodiumhydride (80% strength), and the mixture is stirred at room temperature(about 20° C.) for about 60 minutes. The crystalline product is thenisolated by filtration with suction.

2.0 g (94% of theory) of the sodium salt of5-ethoxy-4-methyl-2-(4-methyl-2-methoxycarbonyl-thien-3-yl-sulfonylaminocarbonyl)-2,4-dihydro-3H-1,2,4-triazol-3-one are obtained as a colourless crystalline product ofmelting point 248° C.

Starting materials of the formula (II):

Example (II-1)

12.0 g (42.6 mmol) of 4-methyl-2-i-propoxycarbonyl-thiophene-3-sulfonylchloride are dissolved in 100 ml of methylene chloride and admixed with8.2 g (85.4 mmol) of ammonium carbonate. The mixture is stirred at roomtemperature (about 20° C.) for, about 24 hours. The undissolved salt isfiltered off by suction, the filtrate is, concentrated using water pumpvacuum, the residue is digested with diethyl ether and the crystallineproduct is isolated by filtration with suction.

9.1 g (91% of theory) of4-methyl-2-i-propoxycarbonyl-thiophene-3-sulphonamide are obtained as alight-yellow solid of melting point 76° C.

Similarly, it is possible to prepare for example the following compoundsof the formula II):

4-methyl-2-methoxycarbonyl-thiophene-3-sulphonamide (mp.: 54° C.),

4-methyl-2-ethoxycarbonyl-thiophene-3-sulphonamide (mp.: 65° C.),

4-methyl-2-n-propoxycarbonyl-thiophene-3-sulphonamide (mp.: 90° C.),

4-methyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

4-ethyl-2-methoxycarbonyl-thiophene-3-sulphonamide,

4-ethyl-2-ethoxycarbonyl-thiophene-3-sulphonamide,

4-ethyl-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

4-ethyl-2-i-propoxycarbonyl-thlophene-3-sulphonamide,

4-ethyl-2-(oxetan-2-yl-oxycarbonyl)-thlophene-3-sulphonamide,

4-fluoro-2-methoxycarbonyl-thiophene-3-sulphonamide,

4-fluoro-2-ethoxycarbonyl-thiophene-3-sulphonamide,

4-fluoro-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

4-fluoro-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

4-fluoro-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

4-chloro-2-methoxycarbonyl-thiophene-3-sulphonamide,

4-chloro-2-ethoxycarbonyl-thiophene-3-sulphonamide,

4-chloro-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

4-chloro-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

4-chloro-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

4-bromo-2-methoxycarbonyl-thiophene-3-sulphonamide,

4-bromo-2-ethoxycarbonyl-thiophene-3-sulphonamide,

4-bromo-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

4-bromo-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

4-bromo-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

4-methoxy-2-methoxycarbonyl-thiophene-3-sulphonamide,

4-methoxy-2-ethoxycarbonyl-thiophene-3-sulphonamide,

4-methoxy-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

4-methoxy-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

4-methoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

4-methylthio-2-methoxycarbonyl-thiophene-3-sulphonamide,

4-methylthio-2-ethoxycarbonyl-thiophene-3-sulphonamide,

4-methylthio-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

4-methylthio-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

4-methylthio-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

4-trifluoromethyl-2-methoxycarbonyl-thiophene-3-sulphonamide,

4-trifluoromethyl-2-ethoxycarbonyl-thiophene-3 -sulphonamide,

4-trifluoromethyl-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

4-trifluoromethyl-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

4-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

4-difluoromethoxy-2-methoxycarbonyl-thiophene-3-sulphonamide,

4-difluoromethoxy-2-ethoxycarbonyl-thiophene-3-sulphonamide,

4-difluoromethoxy-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

4-difluoromethoxy-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

4-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide,

4-trifluoromethoxy-2-methoxycarbonyl-thiophene-3-sulphonamide,

4-trifluoromethoxy-2-ethoxycarbonyl-thiophene-3-sulphonamide,

4-trifluoromethoxy-2-n-propoxycarbonyl-thiophene-3-sulphonamide,

4-trifluoromethoxy-2-i-propoxycarbonyl-thiophene-3-sulphonamide,

4-trifluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonamide.

6-methyl-2-methoxycarbonyl-benzenesulphonamide (mp.: II 8° C.),

6-methyl-2-ethoxycarbonyl-benzenesulphonamide (mp: 277° C.),

6-methyl-2-n -propoxycarbonyl-benzenesulphonamide,

6-methyl-2-i-propoxycarbonyl-benzenesuliphonainide (mp.: 122° C.),

6-methyl-2-(oxetan-2-yl-oxycarbonyl)-benzene sulphonamide,

6-ethyl-2-methoxycarbonyl-benzenesulphonamide,

6-ethyl-2-ethoxycarbonyl-benzenesulphonamide,

6-ethyl-2-n-propoxycarbonyl-benzenesulphonarnide,

6-ethyl-2-1-propoxycarbonyl-benzenesulphonamide,

6-ethyl-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonarnide,

6-fluoro-2-methoxycarbonyl-benzenesulphonamide,

6-fluoro-2-ethoxycarbonyl-benzenesulphonarnide,

6-fluoro-2-n-propoxycarbonyl-benzenesulphonamide,

6-fluoro-2-i-propoxycarbonyl-benzenesulphonamide,

6-fluoro-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

6-chloro-2-methoxycarbonyl-benzenesulphonamide,

6-chloro-2-ethoxycarbonyl-benzenesulphonamide,

6-chloro-2-n-propoxycarbonyl-benzenesulphonamide,

6-chloro-2-i-propoxycarbonyl-benzenesulphonamide,

6-chloro-2-(oxetan-2-yl-oxycarbonyl)-benzene-sulphonamide,

6-bromo-2-methoxycarbonyl-benzenesulphonamide,

6-bromo-2-ethoxycarbonyl-benzenesulphonamide,

6-bromo-2-n-propoxycarbonyl-benzenesulphonamide,

6-bromo-2-i-propoxycarbonyl-benzenesulphonamide,

6-bromo-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

6-methoxy-2-methoxycarbonyl-benzenesulphonamide,

6-methoxy-2-ethoxycarbonyl-benzenesulphonarnide,

6-methoxy-2-n-propoxycarbonyl-benzenesulphonamide,

6-methoxy-2-i-propoxycarbonyl-benzenesulphonamide,

6-methoxy-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

6-methylthio-2-methoxycarbonyl-benzenesulphonamide,

6-methylthio-2-ethoxycarbonyl-benzenesulphonamide,

6-methylthio-2-n-propoxycarbonyl-benzenesulphonamide,

6-methylthio-2-i-propoxycarbonyl-benzenesulphonamide,

6-methylthio-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

6-trifluoromethyl-2-methoxycarbonyl-benzenesulphonamide,

6-trifluoromethyl-2-ethoxycarbonyl-benzenesulphonamide,

6-trifluoromethyl-2-n-propoxycarbonyl-benzenesulphonamide,

6-trifluoromethyl-2-i-propoxycarbonyl-benzenesulphonamide,

6-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide,

6-difluoromethoxy-2-methoxycarbonyl-benzenesulphonamide,

6-difluoromethoxy-2-ethoxycarbonyl-benzenesulphonamide,

6-difluoromethoxy-2-n-propoxycarbonyl-benzenesulphonamide,

6-difluoromethoxy-2-i-propoxycarbonyl-benzenesulphonamide,

6-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonarnide,

6-trifluoromethoxy-2-methoxycarbonyl-benzenesulphonamide,

6-trifluoromethoxy-2-ethoxycarbonyl-benzenesulphonamide,

6-trifluoromethoxy-2-n-propoxycarbonyl-benzenesulphonamide,

6-trifluoromethoxy-2-i-propoxycarbonyl-benzenesulphonamide,

6-trifluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonamide.

Starting materials of the formula (IV):

Example (IV-1)

A mixture of 25 g (95 mmol) of4-methyl-2-methoxycarbonyl-thiophene-3-sulphonamide, 9.4 g (95 mmol) ofn-butyl isocyanate and 100 ml of chlorobenzene is heated to boilingpoint, and at reflux temperature, phosgene is introduced for 4 hours.The mixture is subsequently concentrated using water pump vacuum and theresidue is purified by distillation under reduced pressure (2 mbar).

11 g (40% of theory) of4-methyl-2-methoxycarbonyl-thiophene-3-yl-sulfonyl isocyanate of aboiling range of 140° C.-145° C. (at 2 mbar), which solidify to givecolourless crystals, are obtained.

Similarly, it is possible to prepare for example the following compoundsof the formula (II):

4-methyl-2-ethoxycarbonyl-thiophene-3-yl-sulphonyl isocyanate,

4-methyl-2-n-propoxycarbonyl-thiophene-3-yl-sulphonyl isocyanate,

4-methyl-2-i-propoxycarbonyl-thiophene-3-yl-sulphonyl isocyanate,

4-methyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-yl-sulphonylisocyanate,

4-ethyl-2-methoxycarbonyl-thiophene-3-yl-sulphonyl isocyanate,

4-ethyl-2-ethoxycarbonyl-thiophene-3-yl-sulphonyl isocyanate,

4-ethyl-2-n-propoxycarbonyl-thiophene-3-yl-sulphonyl isocyanate,

4-ethyl-2-i-propoxycarbonyl-thiophene-3-yl-sulphonyl isocyanate,

4-ethyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-yl-sulphonyl isocyanate,

4-fluoro-2-methoxycarbonyl-thiophene-3-yl-sulphonyl isocyanate,

4-fluoro-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-fluoro-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-fluoro-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-fluoro-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

4-chloro-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-chloro-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-chloro-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-chloro-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-chloro-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonyl isocyanate,

4-bromo-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-bromo-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-bromo-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-bromo-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-bromo-2-(oxetan-2yl-oxycarbonyl )-thiophen-3-yl -sulphonyl isocyanate,

4-methoxy-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-methoxy-2-ethoxycarbonyl- thiophen-3-yl-sulphonyl isocyanate,

4-methoxy-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-methoxy-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-methoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-suphony isocyanate,

4-methylthio-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-methylthio-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-methylthio-2-n-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-methylthio-2-i-propoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-methylthio-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3 -yl-sulphonylisocyanate,

4-trifluoromethyl-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-trifluoromethyl-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-trifluoromethyl-2-n-propoxycarbonyl-thiophen-3-yl-sulphonylisocyanate,

4-trifluoromethyl-2-i-propoxycarbonyl-thiophen-3-yl-sulphonylisocyanate,

4-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonylisocyanate,

4-difluoromethoxy-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-difluoromethoxy-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-difluoromethoxy-2-n-propoxycarbonyl-thiophen-3-yl-sulphonylisocyanate,

4-difluoromethoxy-2-i-propoxycarbonyl-thiophen-3-yl-sulphonylisocyanate,

4-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophen-3-yl-sulphonylisocyanate,

4-trifluoromethoxy-2-methoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-trifluoromethoxy-2-ethoxycarbonyl-thiophen-3-yl-sulphonyl isocyanate,

4-trifluoromethoxy-2-n-propoxycarbonyl-thiophen-3-yl-sulphonylisocyanate,

4-trifluoromethoxy-2-i-propoxycarbonyl-thiophen-3-y-sulphonylisocyanate,

4-trifluoromethoxy-2-(oxetan-2-p-oxycarbonyl)-thiophen-3-yl-sulphonylisocyanate,

6-methyl-2-methoxycarbonyl-phenylsulphonyl isocyanate,

6-methyl-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

6-methyl-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

6-methyl-2-i-propoxy carbonyl-phenylsulphonyl isocyanate,

6-methyl- 2-(oxetan-2- yl-oxycarbonyl)- phenylsulphonyl isocyanate,

6-ethyl-2-methoxycarbonyl-phenylsulphonyl isocyanate,

6-ethyl-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

6-ethyl-2-n-propoxycarbonyl-phenysulphonyl isocyanate,

6-ethyl-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

6-ethyl-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

6-fluoro-2-methoxycarbonyl-phenylsulphonyl isocyanate,

6-fluoro-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

6-fluoro-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

6-fluoro-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

6-fluoro-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

6-chloro-2-methoxycarbonyl-phenylsulphonyl isocyanate,

6-chloro-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

6-chloro-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

6-chloro-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

6-chloro-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

6-bromo-2-methoxycarbonyl-phenylsulphonyl isocyanate,

6-bromo-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

6-bromo-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

6-bromo-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

6-bromo-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

6-methoxy-2-methoxycarbonyl-phenylsulphonyl isocyanate,

6-methoxy-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

6-methoxy-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

6-methoxy-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

6-methoxy-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

6-methylthio-2-methoxycarbonyl-phenylsulphonyl isocyanate,

6-methylthio-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

6-methylthio-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

6-methylthio-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

6-methylthio-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonyl isocyanate,

6-trifluoromethyl-2-methoxycarbonyl-phenylsulphonyl isocyanate,

6-trifluoromethyl-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

6-trifluoromethyl-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

6-trifluoromethyl-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

6-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonylisocyanate,

6-difluoromethoxy-2-methoxycarbonyl-phenylsulphonyl isocyanate,

6-difluoromethoxy-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

6-difluoromethoxy-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

6-difluoromethoxy-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

6-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonylisocyanate,

6-trifluoromethoxy-2-methoxycarbonyl-phenylsulphonyl isocyanate,

6-trifluoromethoxy-2-ethoxycarbonyl-phenylsulphonyl isocyanate,

6-trifluoromethoxy-2-n-propoxycarbonyl-phenylsulphonyl isocyanate,

6-trifluoromethoxy-2-i-propoxycarbonyl-phenylsulphonyl isocyanate,

6-trifluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-phenylsulphonylisocyanate.

Starting materials of the formula (VI):

Example (VI-1)

A solution of 21.2 g (90 mmol) of i-propyl3-amino-4-methyl-thiophene-2-carboxylate hydrochloride in 60 ml of conc.hydrochloric acid is cooled to about −10° C., and a solution of 6.9 g(100 mmol) of sodium nitrite in 13 ml of water is then added dropwisewith stirring to this mixture at −10° C. to −5° C. The reaction mixtureis stirred at −5° C. to 0° C. for about 60 minutes. The resultingdiazonium salt solution is added dropwise at about 15° C. to a solutionof 50 g of sulphur dioxide in 110 ml of acetic acid containing 10 ml ofa saturated aqueous solution of copper(II) chloride. The mixture isstirred at room temperature (about 20° C.) for 12 hours and then dilutedwith about 500 ml of methylene chloride, washed twice with ice-water,dried over magnesium sulphate and filtered. The filtrate is concentratedusing water pump vacuum, the residue is digested with petroleum etherand the resulting crystalline product is isolated by filtration withsuction.

17.0 g of (67% of theory) of4-methyl-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride are obtainedas a yellow solid of melting point 58° C.

Similarly, it is possible to prepare for example the following compoundsof the formula (VI):

4-methyl-2-methoxycarbonyl-thiophene-3-sulphonyl chloride (mp.: 56° C.),

4-methyl-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride (mp.: 47° C.),

4-methyl-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride (mp.: 42°C.),

4-methyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

4-ethyl-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

4-ethyl-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

4-ethyl-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-ethyl-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-ethyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

4-fluoro-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

4-fluoro-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

4-fluoro-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-fluoro-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-fluoro-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

4-chloro-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

4-chloro-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

4-chloro-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-chloro-2i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-chloro-2-(oxetan-2-yl-oxycarbonyl )-thiophene-3-sulphonyl chloride,

4-bromo-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

4-bromo-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

4-bromo-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-bromo-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-bromo-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

4-methoxy-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

4-methoxy-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

4-methoxy-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-methoxy-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-methoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

4-methylthio-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

4-methylthio-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

4-methylthio-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-methylthio-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-methylthio-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonyl chloride,

4-trifluoromethyl-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

4-trifluoromethyl-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

4-trifluoromethyl-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-trifluoromethyl-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3-sulphonylchloride,

4-difluoromethoxy-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

4-difluoromethoxy-2-ethoxycarbonyl-thiophene-3-sulphonyl chloride,

4-difluoromethoxy-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-difluoromethoxy-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-thiophene-3 -sulphonylchloride,

4-trifluoromethoxy-2-methoxycarbonyl-thiophene-3-sulphonyl chloride,

4-trifluoromethoxy-2-ethoxycarbonyl-thiophene-3- sulphonyl chloride,

4-trifluoromethoxy-2-n-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-trifluoromethoxy-2-i-propoxycarbonyl-thiophene-3-sulphonyl chloride,

4-trifluoromethoxy-2-(oxetan-2-yl-oxycarbonyl )-thiophene-3-sulphonylchloride,

6-methyl-2-methoxycarbonyl-benzenesulphonyl chloride (mp.: 109° C.),

6-methyl-2-ethoxycarbonyl-benzenesulphonyl chloride (mp.: 82° C.),

6-methyl- 2-n-propoxycarbonyl-benzenesulphonyl chloride (mp.: 52C),

6-methyl- 2-i-propoxycarbonyl-benzenesulphonyl chloride (p.: 51 ° C.),

6-methyl- 2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

6-ethyl-2-methoxycarbonyl-benzenesulphonyl chloride,

6-ethyl-2-ethoxycarbonyl-benzenesulphonyl chloride,

6-ethyl-2-n-propoxycarbonyl-benzenesulphonyl chloride,

6-ethyl-2-i-propoxycarbonyl-benzenesulphonyl chloride,

6-ethyl-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

6-fluoro-2-methoxycarbonyl-benzenesulphonyl chloride,

6-fluoro-2-ethoxycarbonyl-benzenesulphonyl chloride,

6-fluoro-2-n-propoxycarbonyl-benzenesulphonyl chloride,

6-fluoro-2-i-propoxycarbonyl-benzenesulphonyl chloride,

6-fluoro-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

6-chloro-2-methoxycarbonyl-benzenesulphonyl chloride,

6-chloro-2-ethoxycarbonyl-benzenesulphonyl chloride,

6-chloro-2-n-propoxycarbonyl-benzenesulphonyl chloride,

6-chloro-2-i-propoxycarbonyl-benzenesulphonyl chloride,

6-chloro-2-(oxetan-2-yl-oxycarbonyl)-benzene-sulphonyl chloride,

6-bromo-2-methoxycarbonyl-benzenesulphonyl chloride,

6-bromo-2-ethoxycarbonyl-benzenesulphonyl chloride,

6-bromo-2-n-propoxycarbonyl-benzenesulphonyl chloride,

6-bromo-2-i-propoxycarbonyl-benzenesulphonyl chloride,

6-bromo-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

6-methoxy-2-methoxycarbonyl-benzenesulphonyl chloride,

6-methoxy-2-ethoxycarbonyl-benzenesulphonyl chloride,

6-methoxy-2-n-propoxycarbonyl-benzenesulphonyl chloride,

6-methoxy-2-i-propoxycarbonyl-benzenesulphonyl chloride,

6-methoxy-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

6-methylthio-2-methoxycarbonyl-benzenesulphonyl chloride,

6-methylthio-2-ethoxycarbonyl-benzenesulphonyl chloride,

6-methylthio-2-n-propoxycarbonyl-benzenesulphonyl chloride,

6-methylthio-2-i-propoxycarbonyl-benzenesulphonyl chloride,

6-methylthio-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

6-trifluoromethyl-2-methoxycarbonyl-benzenesulphonyl chloride,

6-trifluoromethyl-2-ethoxycarbonyl-benzenesulphonyl chloride(amorphous),

6-trifluoromethyl-2-n-propoxycarbonyl-benzenesulphonyl chloride,

6-trifluoromethyl-2-i-propoxycarbonyl-benzenesulphonyl chloride (mp.:64° C.),

6-trifluoromethyl-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

6-difluoromethoxy-2-methoxycarbonyl-benzenesulphonyl chloride,

6-difluoromethoxy-2-ethoxycarbonyl-benzenesulphonyl chloride,

6-difluoromethoxy-2-n-propoxycarbonyl-benzenesulphonyl chloride,

6-difluoromethoxy-2-i-propoxycarbonyl-benzenesulphonyl chloride,

6-difluoromethoxy-2-(oxetan-2-yl-oxycarbonyl)-benzenesulphonyl chloride,

6-trifluoromethoxy-2-methoxycarbonyl-benzenesulphonyl chloride,

6-trifluoromethoxy-2-ethoxycarbonyl-benzenesulphonyl chloride,

6-trifluoromethoxy-2-n-propoxycarbonyl-benzenesulphonyl chloride,

6-trifluoromethoxy-2--propoxycarbonyl-benzenesulphonyl chloride,

6-trifluoromethoxy-2-(oxetan-2-yl-oxycarbonyl )-benzenesulphonylchloride.

Starting materials of the formula (X):

Example (X-1)

With shaking, a mixture of 192 g (1.43 mol) of i-propyl mercaptoacetateand 183 g (1.43 mol) of i-propyl methacrylate is admixed with 5 drops ofpiperidine. The mixture is heated to 50° C., admixed with a further 20drops of piperidine and stirred at a bath temperature of 100° C. for 12hours. The mixture is subsequently distilled under reduced pressure.

288 g (77% of theory) of i-propyl2-methyl-3-(i-propoxycarbonylmethylthio)-propionate are obtained as acolourless oil of a boiling range of 135° C. to 140° C. at 2 mbar.

Similarly, it is possible to prepare for example the followingcompounds:

methyl 2-methyl-3-(methoxycarbonylmethylthio)-propionate,

ethyl 2-methyl-3-(ethoxycarbonylmethylthio)-propionate (bp.: 105° C. to112° C. at 1 mbar),

n-propyl 2-methyl-3-(n-propoxycarbonylmethylthio)-propionate (bp: 145°C. to 147° C. at 3 mbar),

methyl 2-methyl-3-(ethoxycarbonylmethylthio)-propionate (bp.: 150° C. to152° C. at 0.1 mbar),

methyl 2-methyl-3-(n-propoxycarbonylmethylthio)-propionate (bp.: 158° C.to 160° C. at 0.1 mbar),

methyl 2-methyl-3-(i-propoxycarbonylmethylthio)-propionate (bp.: 162° C.to 165° C. at 0.1 mbar),

methyl 2-ethyl-3-(methoxycarbonylmethylthio)-propionate,

ethyl 2-ethyl-3-(ethoxycarbonylmethylthio)-propionate,

n-propyl 2-ethyl-3-(n-propoxycarbonylmethylthio)-propionate,

i-propyl 2-ethyl-3-(i-propoxycarbonylmethylthio)-propionate,

methyl 2-ethyl-3-(ethoxycarbonylmethylthio)-propionate,

methyl 2-ethyl-3-(n-propoxycarbonylmethylthio)-propionate,

methyl 2-ethyl-3-(i-propoxycarbonylmethylthio)-propionate,

methyl 2-trifluoromethyl-3-(methoxycarbonylmethylthio)-propionate,

ethyl 2-trifluoromethyl-3-(ethoxycarbonylmethylthio)-propionate,

n-propyl 2-trifluoromethyl-3-(n-propoxycarbonylmethylthio)-propionate,

i-propyl 2-trifluoromethyl-3-(i-propoxycarbonylmethylthio)-propionate,

methyl 2-trifluoromethyl-3-(ethoxycarbonylmethylthio)-propionate,

methyl 2-trifluoromethyl-3-(n-propoxycarbonylmethylthio)-propionate,

methyl 2-trifluoromethyl-3-(i-propoxycarbonylmethylthio)-propionate,

methyl 2-chloro-3-(methoxycarbonylmethylthio)-propionate,

ethyl 2-chloro-3-(ethoxycarbonylmethylthio)-propionate,

n-propyl 2-chloro-3-(n-propoxycarbonylmethylthio)-propionate,

i-propyl 2-chloro-3-(i-propoxycarbonylmethylthio)-propionate,

methyl 2-chloro-3-(ethoxycarbonylmethylthio)-propionate,

methyl 2-chloro-3-(n-propoxycarbonylmethylthio)-propionate,

methyl 2-chloro-3-(i-propoxycarbonylmethylthio)-propionate.

At room temperature (about 20° C.), 480 g (1.83 mol) of i-propyl2-methyl-3-(i-propoxycarbonylmethylthio)-propionate are added dropwiseto a suspension of 246 g (3.0 mol) of sodium i-propoxide in 1 litre oftoluene, and the mixture is then stirred at about 90° C. for about 12hours. The mixture is subsequently poured into ice-cold 2N hydrochloricacid. This mixture is then extracted three times with diethyl ether andthe combined extracts are washed twice with water. The organic phase isdried over magnesium sulphate and filtered. The filtrate is concentratedusing water pump vacuum and the residue is distilled under reducedpressure.

254 g (69% of theory) of i-propyl4-methyl-3-oxo-tetrahydrothiophene-2-carboxylate are obtained as alight-yellow oil of boiling point 119° C. to 120° C. at 1 mbar.

Similarly, it is possible to prepare for example the followingcompounds:

methyl 4-methyl-3-oxo-tetrahydrothiophene-2-carboxylate,

ethyl 4-methyl-3-oxo-tetrahydrothiophene-2-carboxylate (bp.: 112° C.at4mbar),

n-propyl 4-methyl-3-oxo-tetrahydrothiophene-2-carboxylate (bp.: 127° C.to 128° C. at 1 mbar),

methyl 4-ethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

ethyl 4-ethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

n-propyl 4-ethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

i-propyl 4-ethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

methyl 4-trifluoromethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

ethyl 4-trifluoromethyl-3-oxo-tetrahydrothiophene -2-carboxylate,

n-propyl 4-trifluoromethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

i-propyl 4-trifluoromethyl-3-oxo-tetrahydrothiophene-2-carboxylate,

methyl 4-chloro-3-oxo-tetrahydrothiophene-2-carboxylate,

ethyl 4-chloro-3-oxo-tetrahydrothiophene-2-carboxylate,

n-propyl 4-chloro-3-oxo-tetrahydrothiophene-2-carboxylate,

i-propyl 4-chloro-3-oxo-tetrahydrothiophene-2-carboxylate.

A mixture of 505 g (2.5 mol) of i-propyl4-methyl-3-oxo-tetrahydrothiophene-2-carboxylate, 497 g (7.2 mol) ofhydroxylamine hydrochloride, 753 g (3.8 mol) of barium carbonate and 2.5litres of isopropanol is heated under reflux for about 12 hours. Themixture is subsequently filtered off with suction, the filter cake iswashed with hot isopropanol and the filtrate is concentrated using waterpump vacuum. The residue is taken up in 2 litres of diethyl ether,washed twice with water, dried over magnesium sulphate and filtered. Thesolvent is carefully distilled off from the filtrate using water pumpvacuum.

445 g (82% of theory) of i-propyl4-methyl-3-hydroximino-tetrahydrothiophene-2-carboxylate are obtained asa light-yellow oily crude product which is employed without any fartherpurification for the next step.

Similarly, it is possible to prepare for example the followingcompounds:

methyl 4-methyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

ethyl 4-methyl-3-hydroximino-tetrahydrothiophene-2-carboxylate(colourless oil),

n-propyl 4-methyl-3-hydroximino-tetrahydrothiophene-2-carboxylate(light-yellow oil),

methyl 4-ethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

ethyl 4-ethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

n-propyl 4-ethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

i-propyl 4-ethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

methyl4-trifluoromethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

ethyl 4-trifluoromethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

n-propyl4-trifluoromethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

i-propyl4-trifluoromethyl-3-hydroximino-tetrahydrothiophene-2-carboxylate,

methyl 4-chloro-3- hydroximino-tetrahydrothiophene-2-carboxylate,

ethyl 4-chloro-3-hydroximino-tetrahydrothiophene-2-carboxylate,

n-propyl 4-chloro-3-hydroximino-tetrahydrothiophene-2-carboxylate,

i-propyl 4-chloro-3-hydroximino-tetrahydrothiophene-2-carboxylate.

334 g (1.54 mol) of i-propyl4-methyl-3-hydroximino-tetrahydrothiophene-2-carboxylate are dissolvedin 5 litres of methyl tert-butyl ether and cooled using an ice bath.Hydrogen chloride is then—after the ice bath had been removed—introducedwith stirring for two hours. The mixture is subsequently concentratedusing water pump vacuum and the amorphous residue is crystallized fromacetone.

358 g (99% of theory) of i-propyl3-amino-4-methyl-thiophene-2-carboxylate hydrochloride are obtained as abeige-coloured solid of melting point 1 53° C.

Similarly, it is possible to prepare for example the followingcompounds:

ethyl 3-amino4-methyl-thiophene-2-carboxylate hydrochloride (mp.: 133°C.),

n-propyl 3-amino-4-methyl-thiophene-2-carboxylate hydrochloride (mp.:152° C.),

ethyl 3-amino-4-ethyl-thiophene-2-carboxylate hydrochloride,

n-propyl 3-amino-4-ethyl-thiophene-2-carboxylate hydrochloride,

i-propyl 3-amino-4-ethyl-thiophene-2-carboxylate hydrochloride,

ethyl 3-amino-4-trifluoromethyl-thiophene-2-carboxylate hydrochloride,

propyl 3-amino-4-trifluoromethylthiophene-2-carboxyate hydrochloride,

i-propyl 3-amino-4-trifluoromethyl-thiophene-2-carboxylatehydrochloride,

ethyl 3-amino-4-chloro-thiophene-2-carboxylate hydrochloride,

n-propyl 3-amino-4-chloro -thiophene-2-carboxylate hydrochloride,

i-propyl 3-amino-4-chloro-thiophene-2-carboxylate hydrochloride.

11.75 g (50 mmol) of i-propyl 3-amino-4-methyl-thiophene-2-carboxylatehydrochloride are dissolved in 100 ml of water. 150 ml of methylenechloride are added to this solution, and sodium bicarbonate is thenadded a little at a time until a pH of 7 has been exceeded. The mixtureis stirred for 8 hours and the organic phase is separated off, washedwith water, dried with magnesium sulphate and filtered. The filtrate isconcentrated using water pump vacuum and the amorphous residue iscrystallized from petroleum ether.

7.2 g (73% of theory) of i-propyl3-amino4-methyl-thiophene-2-carboxylate are obtained as a beige-colouredsolid of melting point 40° C.

Similarly, it is possible to prepare for example the followingcompounds:

ethyl 3-amino-4-methyl-thiophene-2-carboxylate (mp.: 133° C.),

n-propyl 3-amino-4-methyl-thiophene-2-carboxylate (amorphous),

ethyl 3-amino-4-ethyl-thiophene-2-carboxylate,

n-propyl 3-amino-4-ethyl-thiophene-2-carboxylate,

i-propyl 3-amino-4-ethyl-thiophene-2-carboxylate,

ethyl 3-amino-4-trifluoromethyl-thiophene-2-carboxylate,

n-propyl 3-amino-4-trifluoromethyl-thiophene-2-carboxylate,

i-propyl 3-amino-4-trifluoromethyl-thiophene-2-carboxylate,

ethyl 3-amino-4-chloro-thiophene-2-carboxylate,

n-propyl 3-amino-4-chloro-thiophene-2-carboxylate,

i-propyl 3-amino-4-chloro-thiophene-2-carboxylate.

USE EXAMPLES Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of the active compound, 1 part byweight of active compound is mixed with the stated amount of solvent,the stated amount of emulsifier is added and the concentrate is dilutedwith water to the desired concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours,the soil is watered with the preparation of active compound.Advantageously, the amount of water per unit area is kept constant. Theactive compound concentration in the preparation is not important, onlythe active compound application rate per unit area matters.

After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control.

The figures denote:

0%=no action (like untreated control)

100%=total destruction

In this test, very strong activity against weeds is shown, for example,by the compounds of Preparation Examples 1, 3, 5, 6, 7, 8, 9, 10, 12,13, 16, 17, 18, 19, 20, 21, 22, 23, 28, 30, 31, 32, 33, 34, 35, 37, 38,39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 51, 53, 54, 55, 56, 57, 58, 59,61, 62, 63, 64, 65, 66, 67, 68, 70, 72, 76, 77, 80, 81, 82, 84, 85, 86,89, 93, 108, 121, 129, 130, 131, 134, 135, 136, 140, 141, 142, 143, 144,145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158,159, 160, 161, 162, 163, 164, 165, 166, 167 and 172, combined withpredominantly good tolerance by crop plants such as, for example, maizeand soya beans.

“ai.”=active compound (“active ingredient”)

TABLE A Pre-emergence test/Greenhouse Active compound of ApplicationPreparation rate Soya Example (g of ai./ha) Maize beans Lolium PoaSorghum Ambrosia Matricaria Solanum  5 30  0 20 95 95 90 95 95 95  1 3010 — 95 95 90 95 95 95  6 125   0 — 95 95 95 95 95 95  7 60  0  0 95 —95 95 95 —  8 60 30  0 95 90 80 90 95 95  9 125   0 — 80 80 60 95 90 9510 250   0 20 80 90 70 95 95 95 12 125   0  0 80 80 60 95 95 95 13 125 30 — 90 80 70 95 95 90 16 30 —  0 95 95 90 95 95 95 17 30 —  0 80 95 6095 95 95 18 60 10  0 80 95 90 95 95 95 19 60  0  0 95 95 — 95 95 90 20125  10  0 95 95 90 95 95 95 21 125   0  0 95 95 95 95 95 95 22 125  2010 95 95 80 95 95 95 23 125   0  0 — 80 60 90 95 90 28 60  0 — 95 95 9595 95 95 30 30  0 — 95 95 80 95 95 95 31 15 10 — 95 95 80 95 95 95 32 6020 20 95 95 60 95 95 95 33 125  10 — — 90 80 90 95 95 34 60 10  0 60 7080 90 95 90 35 60  0 — 95 95 95 95 100  95 37 60 10 10 90 70 — 80 95 9038 60  0 — 95 70 60 95 95 95 39 60  0 20 95 90 — 95 70 90 40 60 10 30 9095 — 95 95 95 41 60  0 — 60 80 60 95 95 90 42 60 10 10 95 95 — 95 95 9543 60 — 10 95 95 80 95 95 95 44  8 30  0 95 95 95 95 95 95 45 125  10 2090 95 — 95 90 95 46  8  0 — 80 95 80 95 95 95 47 125  10 10 90 90 60 9595 95 48 125  30 20 95 95 — 95 100  95 51 125   0 30 80 80 80 95 95 9553 125   0 — 95 95 — 95 95 95 54 30  0 — 95 95 80 95 95 95 55 125  10 —100  90 60 100  100  100  56 125  —  0 60 80 — — 100  95 57 60  0 — 9595 95 — 95 95 58 125  20 — 80 95 — — 100  95 59 125   0 — 100  70 — 95100  95 61 125   0 — 95 95 80 100  95 95 62 125   0 — 80 90 60 — 95 9563 60 10 — 100  95 80 100  100  100  64 60 10 30 90 60 — 100  100  100 65 125  20 — 80 80 80 — 95 95 66 125   0 — 100  — 100  — 100  100  67 60 0 — 100  — 90 — 100  100  68 125   5 10 80 90 60 95 100  95 70 60 10 —90 90 — 90 100  100  72 125  10 — 90 70 — 95 100  100  76 60  0 30 95 —95 — 100  95 77 60  0 — 95 — 90 — 100  90 80 125   0 — 95 — 90 — 100  9581 60 — — 100  — 95 — 100  100  82 60  0 — 60 — 90 — 100  100  84 125  5 30 95 — 90 — 95 100  85 125  60 — 95 — 95 — 100  100  86 125  10 4080 — 70 — 100  95 89 125   0 — 100  — 90 — 100  100  93 60  0 — 90 — 80— 95 90 108  125   5 — 90 — 95 — 95 90 121  500  10 — 70 — 80 — 90 95129  250  10 10 95 95 90 60 90 95 130  250  10  0 95 95 80 95 95 95 131 250   0  0 95 90 90 95 80 95 134  500   0 20 95 90 70 80 90 95 135  125 — 40 95 95 90 90 90 95 136  125  30 20 95 95 90 80 90 95 140  30 — 10 —95 95 80 80 95 141  15 30  0 90 80 80 90 80 90 142  15 20 10 95 80 — 8080 80 143  60 20  0 90 90 90 80 — 90 144  125  — — 90 90 95 80 95 95145  60  0  0 95 95 95 95 60 95  3 60 10 20 90 70 — 80 95 80 146  60  010 80 90 — 80 80 90 147  15 30  0 95 90 — 70 70 80 148  60 40  0 80 9590 80 80 95 149  125   0 30 95 95 80 95 95 95 150  125  — 10 80 90 80 7080 80 151  15 20 10 90 90 50 80 90 90 152  125  — 20 95 95 95 95 80 95153  125   0 30 — 95 — 95 70 95 154  60  0  0 95 95 95 70 70 90 155  60— 40 95 95 95 90 80 95 156  60  0 10 70 90 70 70 95 70 157  60  0 20 9080 80 95 100  90 158  30 10 — 95 95 60 95 95 95 159  30 10 — 90 95 60 9595 95 160  60 30 10 90 90 60 90 95 90 161  60  0 20 95 95 — 95 95 95162  60 —  0 95 95 90 80 95 95 163   4 20  0 80 95 60 80 — 90 164   8 20 0 95 95 90 100  70 95 165   8  0 10 — 90 70 80 90 80 166  15 40 — 90 9070 80 95 90 167  60 — 30 80 95 95 90 95 90 172  125  — 60 90 95 90 90 9595

Example B

Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amounts of active compound desired per unit area. Theconcentration of the spray liquor is chosen so that the particularamounts of active compound desired are applied in 2000 1 of water/ha.

After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control.

The figures denote:

0% =no action (like untreated control)

100% =total destruction

In this test, very strong activity against weeds is shown, for example,by the compounds of Preparation Examples 1, 5, 6, 7, 28, 30, 31, 32, 38,44, 54, 63, 140, 141, 144, 151, 159, 162, 163, 164, 165 and 166,combined with predominantly good tolerance by crop plants such as, forexample, maize.

TABLE B Post-emergence test/greenhouse Active compound of ApplicationPreparation rate Example (g of ai./ha) Maize Digitaria EchinochloaLolium Sorghum Amaranthus Gallium Matricaria Stellaria  5 30 10 95 80 7090 100  — 95 90  1 125  60 95 95 90 95 100  — 100  100   6 400  20 90 9595 80 100  90 100  100   7 60 15 95 95 95 100  — 95 95 100  28 60 10 9080 60 95 100  80 90 100  30 60 15 90 70 60 95 100  85 100  100  31 30  595 95 90 80 100  80 100  95 32 60 70 70 100  70 95 95 70 80 90 38 60 1070 90 — 95 100  — 95 95 44 60 50 60 90 70 100  100  95 95 — 54 60 30 —95 95 95 100  85 100  100  63 60 — 50 90 70 80 100  90 95 100  140  250 — 95 90 — 95 100  95 90 70 141  30 10 70 90 — 90 100  90 70 95 144  250 — 95 95 70 95 100  95 70 95 151  30 60 90 70 60 90 95 90 90 90 159  60 —60 80 60 70 95 95 100  100  162  60 — 70 80 90 80 — — 60 90 163  60 6080 70 80 95 100  95 100  95 164  60 — 60 80 70 95 100  90 100  95 165 60 — 50 80 50 90 95 95 95 95 166  60 — 70 70 50 90 95 95 100  95

What is claimed is:
 1. A compound of the formula (I)

wherein A represents sulphur or —CH═CH—, Q represents oxygen or sulphur,R¹ represents optionally cyano-, nitro-, halogen- orC₁-C₄-alkoxy-substituted C₁-C₆-alkyl, represents respectively optionallycyano- or halogen-substituted C₂-C₆-alkenyl or C₂-C₆-alkinyl, representsrespectively optionally cyano-, halogen- or C₁-C₄-alkyl-substitutedC₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, R² represents cyano,nitro, halogen, represents respectively optionally cyano-, halogen- orC₁-C₄-alkoxy-substituted C₁-C₄-alkyl, C₁-C₄-alkylthio,C₁-C₄-alkoxy-carbonyl, C₁-C₄-altio, C₁-C₄-alkylsulphinyl orC₁-C₄-alkylsulphonyl, or represents respectively optionally cyano- orhalogen-substituted C₂-C₄-alkenyl, C₂-C₄-alkinyl, C₂-C₄-alkenyloxy orC₂-C₄-alkinyloxy, and R³ represents respectively optionally substitutedheterocyclyl of the formulae below,

in which Q¹ represents oxygen and R⁴ represents optionally fluorine-,chlorine-, bromine-, cyano-, C₁-C₄-alkoxy-, C₁-C₄-alkyl-carbonyl- orC₁-C₄-alkoxy-carbonyl-substituted C₁-C₆-alkyl, represents respectivelyoptionally fluorine-, chlorine- and/or bromine- substitutedC₂-C₆-alkenyl or C₂-C₆-alkinyl, represents respectively optionallyfluorine-, chlorine-, bromine-, cyano-, C₁-C₄-alkoxy- orC₁-C₄-alkoxy-carbonyl-substituted C₁-C₆-alkoxy, C₁-C₆-alkylamino orC₁-C₆-alkyl-carbonyl-amino, represents C₃-C₆-alkenyloxy, representsdi-(C₁ -C₄-alkyl)-amino, represents respectively optionally fluorine-,chlorine-, bromine-, cyano- and/or C₁-C₄-alkyl-substitutedC₃-C₆-cycloalkyl, or C₃-C₆-cycloalkyl-C₁-C₄-alkyl, and R⁵ representshydrogen, hydroxyl, mercapto, amino, cyano, fluorine, chlorine, bromine,iodine, represents optionally fluorine-, chlorine-, bromine-, cyano-,C₁-C₄-alkoxy-, C₁-C₄-alkyl-carbonyl- orC₁-C₄-alkoxy-carbonyl-substituted C₁-C₆-alkyl, represents respectivelyoptionally fluorine-, chlorine- and/or bromine- substitutedC₂-C₆-alkenyl or C₂-C₆-alkinyl, represents respectively optionallyfluorine-, chlorine-, cyano-, C₁-C₄-alkoxy- orC₁-C₄-alkoxy-carbonyl-substituted C₁-C₆-alkoxy, C₁-C₆-alkylthio,C₁-C₆-alkylamino or C₁-C₆-alkyl-carbonylamino, representsC₃-C₆-alkenyloxy, C₃-C₆-alkinyloxy, C₃-C₆-alkenylthio,C₃-C₆-alkinylthio, C₃-C₆-alkenylamino or C₃-C₆-alkinylamino, representsdi-(C₁ -C₄-alkyl)-amino, represents respectively optionally fluorine-,chlorine-, bromine-, cyano- and/or C₁-C₄-alkyl-substitutedC₃-C₆-cycloalkyl, C₅-C₆-cycloalkenyl, C₃-C₆-cycloalkyloxy,C₃-C₆-cycloalkylthio, C₃-C₆-cycloalkylamino,C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkoxy,C₃-C₆-cycloalkyl-C₁-C₄-alkylthio or C₃-C₆-cycloalkyl-C₁-C₄-alkylamino,or represents respectively optionally fluorine-, chlorine-, bromine-,cyano-, nitro-, C₁-C₄-alkyl-, trifluoromethyl-, C₁-C₄-alkoxy- and/orC₁-C₄-alkoxy-carbonyl-substituted phenoxy or phenyl-C₁-C₄-alkoxy, or R⁴and R⁵ together represent optionally branched alkanediyl having 3 to l11carbon atoms, and the sodium, potassium, magnesium, calcium, ammonium,C₁-C₄-alkyl-ammonium, di-(C₁-C₄-alkyl)-ammonium,tri-(C₁-C₄-alkyl)-ammonium, tetra-(C₁-C₄-alkyl)-ammonium,tri-(C₁-C₄-alkyl)-sulphonium, C₅- or C₆-cycloalkyl-ammonium anddi-(C₁-C₂-alkyl)-benzyl-ammonium salts of compound of the formula (I).2. A compound of the formula (I) according to claim 1, wherein Arepresents sulphur or —CH═CH—, Q represents oxygen or sulphur, R¹represents respectively optionally cyano-, fluorine-, chlorine-,methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- ors-butyl, represents respectively optionally cyano-, fluorine- orchlorine-substituted propenyl, butenyl, propinyl or butinyl, representsrespectively optionally cyano-, fluorine-, chlorine-, methyl- orethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl orcyclo-hexylmethyl, R² represents cyano, fluorine, chlorine, bromine,represents respectively optionally cyano-, fluorine-, chlorine-,methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- ors-butyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl,ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio,methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, orrepresents respectively optionally cyano-, fluorine- orchlorine-substituted propenyl, butenyl, propinyl, butinyl, propenyloxyor propinyloxy, and R³ represents respectively optionally substitutedheterocyclyl of the formulae below,

in which Q¹ represents oxygen and R⁴ represents respectively optionallyfluorine-, chlorine-, cyano-, methoxy- or ethoxy- substituted methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectivelyoptionally fluorine-, chlorine- or bromine- substituted propenyl,butenyl, propinyl or butinyl, represents respectively optionallyfluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy,ethoxy, n- or i-propoxy, n-, i-, s- or t- butoxy, methylamino,ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, representspropenyloxy or butenyloxy, represents dimethylamino or diethylamino,represents respectively optionally fluorine-, chlorine-, methyl- and/orethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl orcyclohexyimethyl, and R⁵ represents hydrogen, hydroxyl, mercapto, amino,fluorine, chlorine, bromine, represents respectively optionallyfluorine-, chlorine-, cyano-, methoxy- or ethoxy-substituted methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents respectivelyoptionally fluorine-, chlorine- or bromine-substituted ethenyl,propenyl, butenyl, propinyl or butinyl, represents respectivelyoptionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substitutedmethoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio,ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino,ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, representspropenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio,propadienylthio butenylthio, propinylthio, butinylthio, propenylamino,butenylamino, propinylamino or butinylamino, represents dimethylamino,diethylamino or dipropylamino, represents respectively optionallyfluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl,cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy,cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio,cyclopropylarnino, cyclobutylamino, cyclopentylamino, cyclohexylamino,cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl,cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy,cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio,cyclobutylmethylthio, cyclopentyl-methylthio, cyclohexylmethylthio,cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino orcyclohexyl-methylamino, or represents respectively optionally fluorine-,chlorine-, methyl-, trifluoromethyl-, methoxy- and/ormethoxy-carbonyl-substituted phenoxy, benzyloxy, or R⁴ and R⁵ togetherrepresent optionally branched alkanediyl having 3 to 11 carbon atoms. 3.A compound of the formula (I) according to claim 1, wherein A representssulphur or —CH═CH—, Q represents oxygen or sulphur, R¹ representsmethyl, ethyl, n- or i-propyl, 2-cyano-ethyl, 2-fluoro-ethyl,2,2-difluoro-ethyl, 2,2,2-trifluoro-ethyl, 2-chloro-ethyl,2,2-dichloro-ethyl, 2,2,2-trichloro-ethyl, 2-methoxy-ethyl, or2-ethoxy-ethyl, R² represents fluorine, chlorine, bromine, methyl,ethyl, n- or i-propyl, n-, i- or s-butyl, trifluoromethyl, methoxy,ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy ortrifluoroethoxy, and R³ represents optionally substituted triazolinyl ofthe formula below

in which Q¹ represents oxygen or sulphur and R⁴ represents respectivelyoptionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl,ethyl, n- or i-propyl, represents respectively optionally fluorine- orchlorine-substituted propenyl or propinyl, represents methoxy,. ethoxy,n- or i-propoxy, methylamino, ethylamino, n- or i-propylamino,represents propenyloxy, represents dimethylamino or representscyclopropyl, R⁵ represents chlorine or bromine, represents respectivelyoptionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy-substitutedmethyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, representsrespectively optionally fluorine-, chlorine- or bromine-substitutedethenyl, propenyl, butenyl, propinyl or butinyl, represents respectivelyoptionally fluorine-, chlorine-, cyano-, methoxy- or ethoxy- subsitutedmethoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio,ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino,ethylamino, n- or i-propylamino, n-, i-, s- or t- butylamino, representspropenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio,propadienylthio, butenylthio, propinylthio, butinylthio, propenylamino,butenylamino, propinylamino or butinylamino, represents dimethylamino,diethylamino or dipropylamino, represents respectively optionallyfluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl,cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy,cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio,cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino,cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl,cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy,cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio,cyclobutylmethylthio, cyclopentyl-methylthio, cyclohexylmethylthio,cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino orcyclohexyl-methylamino, or represents respectively optionally fluorine-,chlorine-, methyl-, trifluoromethyl-, methoxy- and/ormethoxycarbonyl-substituted phenoxy, benzyloxy, or R⁴ and R⁵ togetherrepresent optionally branched alkanediyl having 3 to 11 carbon atoms. 4.A process for preparing compounds of the formula (I) according to claim1, wherein (a) sulphonamides of the formula (II)

in which A, R¹ and R² are each as defined in claim 1, are reacted with(thio)carboxylic acid derivatives of the formula (III)

in which Q and R³ are each as defined in claim 1 and Z representshalogen, alkoxy, aryloxy or arylalkoxy, optionally in the presence of anacid acceptor and optionally in the presence of a diluent, and thecompounds of the formula (I) obtained by process (a), or (e) are, ifdesired, converted into salts by customary methods.
 5. A herbicidalcomposition comprising a herbicidally effective amount of a compoundaccording to claim 1 and an extender or surfactant.
 6. A method ofcontrolling unwanted vegetation which comprises applying to suchvegetation, or to a locus from which it is desired to exclude suchvegetation, a herbicidally effective amount of a compound according toclaim 1.